Photoreactive polymer and alignment layer comprising the same

ABSTRACT

Disclosed therein are a photoreactive polymer, and an alignment layer comprising the same that exhibit excellences in alignment rate and alignment stability. The photoreactive polymer comprises a cyclic olefin-based repeating unit with at least one photoreactive substituent, and the maximum absolute value of a variation in dichloric ratio per unit UV dose as given by d(dichloric ratio)/d(mJ/cm 2 ) upon exposure to a polarized UV radiation having a wavelength of 150 to 450 nm at a total exposure dose of 20 mJ/cm 2  or less is at least 0.003.

FIELD OF THE INVENTION

The present invention relates to a photoreactive polymer and analignment layer comprising the same and, more particularly, to aphotoreactive polymer and an alignment layer comprising the same thatexhibit excellences in alignment rate and alignment stability.

BACKGROUND ART

With a recent advent of large-sized LCDs and a gradual expansion oftheir usage from portable devices, such as mobile phones, lap-topcomputers, etc., to home appliances, such as wall mounted flat panelTVs, there is a demand for LCDs with high definition and wide viewingangle. In particular, TFT-driven thin film transistor LCDs (TFT-LCDs) ofwhich each pixel is independently driven are much superior in responsespeed of liquid crystals, realizing high-definition motion pictures, andthus increasingly used in a wider range of applications.

To be used as optical switches in the TFT-LCDs, liquid crystals arerequired to be initially aligned in a defined direction on a layerincluding innermost TFT of the display cell. For this, a liquid crystalalignment layer is used.

For the liquid crystal alignment to occur, a heat-resistant polymer suchas polyimide is applied on a transparent glass to form a polymeralignment layer, which is then subjected to a rubbing process using arotary roller wound with a rubbing cloth of nylon or rayon fabrics at ahigh rotation speed to align liquid crystals.

However, the rubbing process remains mechanical scratches on the surfaceof the liquid crystal alignment layer or generates strong staticelectricity, possibly destroying the TFTs. Further, fine fibers comingfrom the rubbing cloth may cause defectives, which become an obstacle toacquiring a higher production yield.

To overcome the problems with the rubbing process and achieve innovationin the aspect of production yield, there has been derived a liquidcrystal alignment method using a light such as UV radiation(hereinafter, referred to as “photo-alignment”).

Photo-alignment refers to the mechanism using a linearly polarized UVradiation to cause the photoreactive groups of a defined photoreactivepolymer to participate in a photoreaction, aligning the main chain ofthe polymer in a defined direction to form a photo-polymerized liquidcrystal alignment layer with aligned liquid crystals.

The representative example of the photo-alignment isphotopolymerization-based photo-alignment as disclosed by M. Schadt etal. (Jpn. J. Appl. Phys., Vol 31., 1992, 2155), Dae S. Kang et al. (U.S.Pat. No. 5,464,669), and Yuriy Reznikov (Jpn. J. Appl. Phys. Vol. 34,1995, L1000). The photo-aligned polymers used in these patent andresearch papers are mostly polycinnamate-based polymers, such aspoly(vinylcinnamate) (PVCN) or poly(vinyl methoxycinnamate) (PVMC). Forphoto-alignment of polymers, the double bond of cinnamate exposed to UVradiation participates in a [2+2] cycloaddition reaction to formcyclobutane, which provides anisotropy to cause liquid crystal moleculesaligned in one direction, inducing liquid crystal alignment.

Besides, JP11-181127 discloses a polymer and an alignment layerincluding the same in which the polymer has a side chain includingphotoreactive groups such as cinnamate on a main chain such as acrylate,methacrylate, etc. Korean Patent Laid-Open Publication No. 2002-0006819also discloses the use of an alignment layer comprising apolymethacryl-based polymer.

However, the above-mentioned conventional photoreactive polymers foralignment layer have a low thermal stability of the polymer main chain,undesirably deteriorating the stability of the alignment layer orproviding poor characteristics in regard to photoreactivity, liquidcrystal alignment, or alignment rate. Particularly, the initialalignment rate after irradiation is not high enough, causing adeterioration in the economical efficiency of the process, and thealignment characteristic is ready to change after a defined period oftime under irradiation to deteriorate the alignment stability.Consequently, it is difficult not only to provide the final alignmentlayer with a uniform alignment characteristic but to efficiently acquirethe alignment layer having a desired good alignment characteristic.

SUMMARY OF THE INVENTION

The present invention provides a photoreactive polymer havingexcellences in alignment rate and alignment stability.

The present invention also provides an alignment layer and a displaydevice that comprise the photoreactive polymer.

The present invention provides a photoreactive polymer that comprises acyclic olefin-based repeating unit with at least one photoreactivesubstituent and is at least 0.003 in the maximum absolute value of avariation in dichloric ratio per unit UV dose (mJ/cm²) as given byd(dichloric ratio)/d(mJ/cm²) upon exposure to a polarized UV radiationhaving a wavelength of 150 to 450 nm at a total exposure dose of 20mJ/cm² or less.

As for the photoreactive polymer, the absolute value of a variation indichloric ratio per unit UV dose (mJ/cm²) as given by d(dichloricratio)/d(mJ/cm²) upon exposure to a polarized UV radiation at a totalexposure dose of 500 mJ/cm² or more may be in the range of 0 to 0.00006.

[15] In the photoreactive polymer, the cyclic olefin-based repeatingunit may comprise a repeating unit of the following formula 3a or 3b:

In the formulas 3a and 3b, independently, m is 50 to 5,000; q is aninteger from 0 to 4; and at least one of R1, R2, R3 and R4 is any oneselected from the group consisting of radicals represented by thefollowing formula 1a or 1b. Among the R1 to R4, the remainders otherthan the radical of the formula 1a or 1b are the same as or differentfrom one another and independently selected from the group consisting ofhydrogen; halogen; substituted or unsubstituted linear or branched alkylhaving 1 to 20 carbon atoms; substituted or unsubstituted linear orbranched alkenyl having 2 to 20 carbon atoms; substituted orunsubstituted linear or branched alkynyl having 2 to 20 carbon atoms;substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms; and apolar functional group comprising at least one of oxygen, nitrogen,phosphor, sulfur, silicon, and boron. When the R1 to R4 are nothydrogen, halogen, or a polar functional group, at least one of a R1 andR2 coordination and a R3 and R4 coordination is bonded to each other toform an alkylidene group having 1 to 10 carbon atoms; or R1 or R2 isbonded to either R3 or R4 to form a saturated or unsaturated aliphaticring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24carbon atoms.

In the formulas 1a and 1b, A is chemical bond, oxygen, sulfur, or —NH—.B is selected from the group consisting of chemical bond, substituted orunsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, carboxy,ester, substituted or unsubstituted arylene having 6 to 40 carbon atoms,and substituted or unsubstituted heteroarylene having 6 to 40 carbonatoms; X is oxygen or sulfur; R9 is selected from the group consistingof chemical bond, substituted or unsubstituted alkylene having 1 to 20carbon atoms, substituted or unsubstituted alkenylene having 2 to 20carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 12carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbonatoms, substituted or unsubstituted aralkylene having 7 to 15 carbonatoms, and substituted or unsubstituted alkynylene having 2 to 20 carbonatoms. At least one of R10 to R14 is a radical represented by-L-R15-R16-(substituted or unsubstituted C6-C40 aryl). Among the R10 toR14, the remainders other than the radical of -L-R15-R16-(substituted orunsubstituted C6-C40 aryl) are the same as or different from one anotherand independently selected from the group consisting of hydrogen;halogen; substituted or unsubstituted alkyl having 1 to 20 carbon atoms;substituted or unsubstituted alkoxy having 1 to 20 carbon atoms;substituted or unsubstituted aryloxy having 6 to 30 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms; andheteroaryl having 6 to 40 carbon atoms with a hetero element in Group14, 15 or 16. L is selected from the group consisting of oxygen, sulfur,—NH—, substituted or unsubstituted alkylene having 1 to 20 carbon atoms,carbonyl, carboxy, —CONH—, and substituted or unsubstituted arylenehaving 6 to 40 carbon atoms. R15 is substituted or unsubstituted alkylhaving 1 to 10 carbon atoms. R16 is selected from the group consistingof chemical bond, —O—, —C(═O)O—, —OC(═O)—, —NH—, —S—, and —C(═O)—.

The present invention also provides an alignment layer comprising thephotoreactive polymer.

The present invention also provides a display device comprising thealignment layer.

The photoreactive polymer of the present invention is far superior inthe initial alignment rate to the conventional photoreactive polymersand not ready to change significantly in the alignment characteristicunder exposure to a UV radiation at a relatively great exposure dose formore than a defined period of time, thereby securing good alignmentstability.

Hence, the use of the photoreactive polymer may efficiently provide analignment layer having a desired good alignment characteristic withuniformity.

Accordingly, the photoreactive polymer can be preferably used as aphoto-aligned polymer in various coating compositions and alignmentlayers formed from the coating compositions applicable to various LCDdevices, and the alignment layer comprising the photoreactive polymermay have excellent characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing an exemplary structure of ageneral alignment layer.

FIG. 2 is a graph showing the change of a variation in dichloric ratioper unit UV dose as given by d(dichloric ratio)/d(mJ/cm²) for thephotoreactive polymers of examples and comparative examples underexposure to a UV radiation at a total exposure dose of 250 mJ/cm² orless in the experimental example.

FIG. 3 is a graph showing the change of a variation in dichloric ratioper unit UV dose as given by d(dichloric ratio)/d(mJ/cm²) for thephotoreactive polymers of examples and comparative examples underexposure to a UV radiation at a total exposure dose of 500 mJ/cm² ormore in the experimental example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, a detailed description will be given as to a photoreactivepolymer and an alignment layer according to embodiments of theinvention.

In accordance with one embodiment of the present invention, there isprovided a photoreactive polymer that comprises a cyclic olefin-basedrepeating unit with at least one photoreactive substituent and is atleast 0.003 in the maximum absolute value of a variation in dichloricratio per unit UV dose as given by d(dichloric ratio)/d(mJ/cm²) uponexposure to a polarized UV radiation having a wavelength of 150 to 450nm at a total exposure dose of 20 mJ/cm² or less.

The photoreactive polymer according to one embodiment of the presentinvention, upon exposure to a polarized UV radiation having a definedwavelength, may have the dichloric ratio even abruptly changing even ata relatively low exposure dose of the polarized UV radiation. Such anexposure to a polarized radiation at a low exposure dose for a shortperiod of time may also result in a rapid change of the dichloric ratio,which reflects the alignment characteristic, so the maximum absolutevalue of a variation in dichloric ratio per unit UV dose as given byd(dichloric ratio)/d(mJ/cm²) is abruptly increased up to at least about0.003, preferably about 0.003 to 0.008, more preferably about 0.005 to0.008 within a short period of time. In contrast, the conventionalphotoreactive polymers are mostly less than about 0.002 or 0.003 in themaximum absolute value of the variation, d(dichloric ratio)/d(mJ/cm²),and far inferior in the change rate of the dichloric ratio to thephotoreactive polymer of the present invention.

Contrarily, the photoreactive polymer according to one embodiment of thepresent invention undergoes photo-alignment at a very high rate uponexposure to a polarized UV radiation, within a short period of time at alow exposure dose relative to any conventional photoreactive polymers.Hence, the use of the photoreactive polymer with such a high alignmentrate may efficiently provide an alignment layer having a desiredalignment characteristic.

More specifically, as for the photoreactive polymer according to oneembodiment of the present invention, the absolute value of a variationin dichloric ratio per unit UV dose as given by d(dichloricratio)/d(mJ/cm²) upon exposure to a polarized UV radiation having awavelength of 150 to 450 nm at a total exposure dose of 20 mJ/cm² mayamount to about 0.003 to 0.008, preferably about 0.005 to 0.008. Inother words, the photoreactive polymer, upon exposure to a polarized UVradiation for a relatively short period of time at a total exposure doseof 20 mJ/cm², may be at least about 0.003 in the absolute value ofd(dichloric ratio)/d(mJ/cm²), consequently with an abrupt change in thedichloric ratio. As a result, the photoreactive polymer undergoesphoto-alignment at a very high rate upon exposure to a polarized UVradiation to very efficiently form an alignment layer having a desiredalignment characteristic.

Also, the photoreactive polymer, under exposure to the polarized UVradiation at a total exposure dose of 500 mJ/cm² or more, may have theabsolute value of a variation in dichloric ratio per unit UV dose asgiven by d(dichloric ratio)/d(mJ/cm²) in the range of about 0 to0.00006, preferably about 0 to 0.00002. More specifically, at a totalexposure dose of 500 to 2,500 mJ/cm², the absolute value of a variationin dichloric ratio per unit UV dose as given by d(dichloricratio)/d(mJ/cm²) may range from about 0 to 0.00006, preferably about 0to 0.00002.

Such a photoreactive polymer may show a desired alignment characteristicstably maintained even when the total exposure dose of the polarized UVradiation amounts to about 500 mJ/cm² or more, for example, about 500 to2,500 mJ/cm² after a long-term irradiation. This implies the fact thatthe photoreactive polymer can maintain an alignment characteristic withhigh stability once the alignment characteristic comes to a definedlevel rapidly in the early stage of exposure. Hence, the use of thephotoreactive polymer makes it possible to provide an alignment layerwith a high alignment stability. In other words, the desired alignmentcharacteristic, once acquired, can be stably maintained without a changeeven when the conditions for the photo-alignment process are changed, sothe use of the photoreactive polymer may provide an alignment layerhaving a desired alignment characteristic uniformly in a stable andefficient way.

On the other hand, the above-described characteristic related to avariation in the dichloric ratio per unit exposure dose (mJ/cm²), whichhas never been offered by the conventional photoreactive polymers, maybe acquired using the photoreactive polymer obtained from the novelcyclic olefin compound.

Hereinafter, a detailed description will be given as to the cyclicolefin compound, the photoreactive polymer, and a preparation method forthe same.

The characteristics of the photoreactive polymer according to oneembodiment of the present invention may be acquired from a photoreactivepolymer obtained from a cyclic olefin compound having a photoreactivegroup of the following formula 1 used as a monomer:

In the formula 1, q is an integer from 0 to 4; and at least one of R1,R2, R3 and R4 is any one selected from the group consisting of radicalsof the following formula 1a and 1b. Among the R1 to R4, the remaindersother than the radical of the formula 1a or 1b are the same as ordifferent from one another and independently selected from the groupconsisting of hydrogen; halogen; substituted or unsubstituted linear orbranched alkyl having 1 to 20 carbon atoms; substituted or unsubstitutedlinear or branched alkenyl having 2 to 20 carbon atoms; substituted orunsubstituted linear or branched alkynyl having 2 to 20 carbon atoms;substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms; and apolar functional group comprising at least one of oxygen, nitrogen,phosphor, sulfur, silicon, and boron. When the R1 to R4 are nothydrogen, halogen, or a polar functional group, at least one of a R1 andR2 coordination and a R3 and R4 coordination is bonded to each other toform an alkylidene group having 1 to 10 carbon atoms; or R1 or R2 isbonded to either R3 or R4 to form a saturated or unsaturated aliphaticring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24carbon atoms.

In the formula 1a or 1b, A is chemical bond, oxygen, sulfur, or —NH—. Bis selected from the group consisting of chemical bond, substituted orunsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, carboxy,ester, substituted or unsubstituted arylene having 6 to 40 carbon atoms,and substituted or unsubstituted heteroarylene having 6 to 40 carbonatoms. X is oxygen or sulfur. R9 is selected from the group consistingof chemical bond, substituted or unsubstituted alkylene having 1 to 20carbon atoms, substituted or unsubstituted alkenylene having 2 to 20carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 12carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbonatoms, substituted or unsubstituted aralkylene having 7 to 15 carbonatoms, and substituted or unsubstituted alkynylene having 2 to 20 carbonatoms. At least one of R10 to R14 is a radical represented by-L-R15-R16-(substituted or unsubstituted C6-C40 aryl). Among the R10 toR14, the remainders other than the radical of -L-R15-R16-(substituted orunsubstituted C6-C40 aryl) are the same as or different from one anotherand independently selected from the group consisting of hydrogen;halogen; substituted or unsubstituted alkyl having 1 to 20 carbon atoms;substituted or unsubstituted alkoxy having 1 to 20 carbon atoms;substituted or unsubstituted aryloxy having 6 to 30 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms; andheteroaryl having 6 to 40 carbon atoms with a hetero element in Group14, 15 or 16. L is selected from the group consisting of oxygen, sulfur,—NH—, substituted or unsubstituted alkylene having 1 to 20 carbon atoms,carbonyl, carboxy, —CONH—, and substituted or unsubstituted arylenehaving 6 to 40 carbon atoms. R15 is substituted or unsubstituted alkylhaving 1 to 10 carbon atoms. R16 is selected from the group consistingof chemical bond, —O—, —C(═O)O—, —OC(═O)—, —NH—, —S—, and —C(═O)—.

In such a cyclic olefin compound, the radical of -L-R15-R16-(substitutedor unsubstituted C6-C40 aryl) may be represented by the followingformula 2, where the linker L is oxygen and the aryl is phenyl; or maybe any radical having a different aryl and a different linker L:

In the formula 2, R15 and R16 are as defined in formula 1; and R17 toR21 are the same as or different from one another and independentlyselected from the group consisting of hydrogen; halogen; substituted orunsubstituted alkyl having 1 to 20 carbon atoms; substituted orunsubstituted alkoxy having 1 to 20 carbon atoms; substituted orunsubstituted aryloxy having 6 to 30 carbon atoms; substituted orunsubstituted aryl having 6 to 40 carbon atoms; heteroaryl having 6 to40 carbon atoms with a hetero element in Group 14, 15 or 16; andsubstituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms.

Such a compound has a chemical structure in which the ends ofphotoreactive groups such as cinnamate are bonded to a substituentrepresented by -L-R15-R16-(substituted or unsubstituted C6-C40 aryl).The substituent comprises an aralkyl structure that alkyl and arylgroups are sequentially connected together via a linker L. Such a bulkychemical structure as aralkyl is connected to the ends of photoreactivegroups via a linker L, confirming the formation of a large free volumebetween the photoreactive groups. This seems likely to be caused by thesteric hindrance between adjacent bulky aralkyl structures.

For this reason, photoreactive groups such as cinnamate in thephotoreactive polymer and the alignment layer prepared using the cyclicolefin compound are relatively free to move (flow) or react in such alarge free volume, minimizing hindrance from other reactors orsubstituents. Consequently, the photoreactive groups in thephotoreactive polymer and the alignment layer can have excellences inphotoreactivity, alignment rate, and photo-alignment. Especially,photoreactive groups such as cinnamate undergo photo-alignment, whichtakes place as a simultaneous occurrence of dimerization andisomerization caused by polarized radiation. The photo-alignment occursmore easily and rapidly without any hindrance in the large free volume.Further, once the photo-alignment occurs, the desired photo-alignmentcharacteristic can be maintained stably without any hindrance from otherphotoreactive groups, or the like.

Accordingly, the photoreactive polymer prepared from the cyclic olefincompound is enabled to realize the characteristics of the embodiment ofthe present invention and have better excellences in alignment rate andalignment stability.

In the cyclic olefin compound, a polar functional group used as asubstituent for the R1 to R4, that is, a polar functional groupincluding at least one of oxygen, nitrogen, phosphor, sulfur, silicon,and boron may be selected from the group consisting of the followingfunctional groups, or otherwise, comprise at least one of oxygen,nitrogen, phosphor, sulfur, silicon, and boron:

—OR₆, —OC(O)OR₆, —R₅OC(O)OR₆, —C(O)OR₆, —R₅C(O)OR₆, —C(O)R₆, —R₅C(O)R₆,—OC(O)R₆, —R₅OC(O)R₆, —(R₅O)p-OR₆, —(OR₅)p-OR₆, —C(O)—O—C(O)R₆,—R₅C(O)—O—C(O)R₆, —SR₆, —R₅SR₆, —SSR₆, —R₅SSR₆, —S(═O)R₆, —R₅S(═O)R₆,—R₅C(═S)R₆—, —R₅C(═S)SR₆, —R₅SO₃R₆, —SO₃R₆, —R₅N═C═S, —N═C═S, —NCO,—R₅—NCO, —CN, —R₅CN, —NNC(═S)R₆, —R₅NNC(═S)R₆, —NO₂, —R₅NO₂,

In the polar functional groups, independently, p is an integer from 1 to10. R5 is substituted or unsubstituted linear or branched alkylenehaving 1 to 20 carbon atoms; substituted or unsubstituted linear orbranched alkenylene having 2 to 20 carbon atoms; substituted orunsubstituted linear or branched alkynylene having 2 to 20 carbon atoms;substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms;substituted or unsubstituted arylene having 6 to 40 carbon atoms;substituted or unsubstituted carbonyloxylene having 1 to 20 carbonatoms; or substituted or unsubstituted alkoxylene having 1 to 20 carbonatoms. R6, R7 and R8 are independently selected from the groupconsisting of hydrogen; halogen; substituted or unsubstituted linear orbranched alkyl having 1 to 20 carbon atoms; substituted or unsubstitutedlinear or branched alkenyl having 2 to 20 carbon atoms; substituted orunsubstituted linear or branched alkynyl having 2 to 20 carbon atoms;substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms;substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; andsubstituted or unsubstituted carbonyloxy having 1 to 20 carbon atoms.

In the cyclic olefin compound, the substituted or unsubstituted arylhaving 6 to 40 carbon atoms or the heteroaryl having 6 to 40 carbonatoms with an hetero element in Group 14, 15 or 16 is selected from thegroup consisting of the following functional groups; or may be otherdifferent aryl or heteroaryl groups:

In the functional groups, R□10 to R□18 are the same as or different fromone another and independently selected from the group consisting ofsubstituted or unsubstituted linear or branched alkyl having 1 to 20carbon atoms; substituted or unsubstituted alkoxy having 1 to 20 carbonatoms; substituted or unsubstituted aryloxy having 6 to 30 carbon atoms;and substituted or unsubstituted aryl having 6 to 40 carbon atoms.

In the cyclic olefin compound, at least one of the R1 to R4 of theformula 1 is a photoreactive group of the formula 1a or 1b. For example,at least one of R1 and R2 may be the photoreactive group. The use of thecyclic olefin compound enables the preparation of a photoreactivepolymer having good characteristics such as an alignment characteristicor the like.

In the above-described structure of the cyclic olefin compound, therespective substituents are defined as follows:

The term “alkyl” as used herein refers to a monovalent linear orbranched saturated hydrocarbon portion having 1 to 20 carbon atoms,preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.The alkyl group inclusively refers to alkyl groups unsubstituted oradditionally substituted with a specific substituent, which will bedescribed later. The examples of the alkyl group may comprise methyl,ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl,dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, iodomethyl, bromomethyl, etc.

The term “alkenyl” as used herein refers to a monovalent linear orbranched hydrocarbon portion having 2 to 20 carbon atoms, preferably 2to 10 carbon atoms, more preferably 2 to 6 carbon atoms with at leastone carbon-carbon double bond. The alkenyl group may form a bondingthrough carbon atoms including a carbon-carbon double bond or throughsaturated carbon atoms. The alkenyl group inclusively refers to alkenylgroups unsubstituted or additionally substituted with a specificsubstituent, which will be described later. The examples of the alkenylgroup may comprise ethenyl, 1-propenyl, 2-propenyl, 2-butenyl,3-butenyl, pentenyl, 5-hexenyl, dodecenyl, etc.

The term “cycloalkyl” as used herein refers to a monovalent saturated orunsaturated mono-, bi- or tri-cyclic non-aromatic hydrocarbon portionhaving 3 to 12 ring-carbon atoms. The cycloalkyl group inclusivelyrefers to cycloalkyl groups additionally substituted with a specificsubstituent, which will be described later. The examples of thecycloalkyl group may comprise cyclopropyl, cyclobutyl, cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl,decahydronaphthalenyl, adamantyl, norbornyl (i.e.,bicyclo[2,2,1]hept-5-enyl), etc.

The term “aryl” as used herein refers to a monovalent mono-, bi- ortri-cyclic aromatic hydrocarbon portion having 6 to 40 ring-carbonatoms, preferably 6 to 12 ring-carbon atoms. The aryl group inclusivelyrefers to aryl groups additionally substituted with a specificsubstituent, which will be described later. The examples of the arylgroup may comprise phenyl, naphthalenyl, fluorenyl, etc.

The term “alkoxyaryl” as used herein refers to the above-defined arylgroup in which at least one hydrogen atom is substituted by an alkoxygroup. The examples of the alkoxyaryl group may comprise methoxyphenyl,ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hextoxyphenyl,heptoxy, octoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl,methoxyfluorenyl, methoxyanthracenyl, etc.

The term “aralkyl” as used herein refers to the above-defined alkylgroup in which at least one hydrogen atom is substituted by an arylgroup. The aralkyl group inclusively refers to aralkyl groupsadditionally substituted with a specific substituent, which will bedescribed later. The examples of the aralkyl may comprise benzyl,benzhydryl, trityl, etc.

The term “alkynyl” as used herein refers to a monovalent linear orbranched hydrocarbon portion having 2 to 20 carbon atoms, preferably 2to 10 carbon atoms, more preferably 2 to 6 carbon atoms with at leastone carbon-carbon triple bond. The alkynyl group may form a bondingthrough carbon atoms including a carbon-carbon triple bond or throughsaturated carbon atoms. The alkynyl group inclusively refers to alkynylgroups additionally substituted with a specific substituent, which willbe described later. The examples of the alkynyl group may compriseethynyl, propynyl, etc.

The term “alkylene” as used herein refers to a divalent linear orbranched saturated hydrocarbon portion having 1 to 20 carbon atoms,preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.The alkylene group inclusively refers to alkylene groups additionallysubstituted with a specific substituent, which will be described later.The examples of the alkylene group may comprise methylene, ethylene,propylene, butylene, hexylene, etc.

The term “alkenylene” as used herein refers to a divalent linear orbranched hydrocarbon portion having 2 to 20 carbon atoms, preferably 2to 10 carbon atoms, more preferably 2 to 6 carbon atoms with at leastone carbon-carbon double bond. The alkenylene group may form a bondingthrough carbon atoms including a carbon-carbon double bond and/orthrough saturated carbon atoms. The alkenylene group inclusively refersto alkenylene groups additionally substituted with a specificsubstituent, which will be described later.

The term “cycloalkylene” as used herein refers to a divalent saturatedor unsaturated mono-, bi- or tri-cyclic non-aromatic hydrocarbon portionhaving 3 to 12 ring-carbon atoms. The cycloalkylene group inclusivelyrefers to cycloalkylene groups additionally substituted with a specificsubstituent, which will be described later. The examples of thecycloalkylene group may comprise cyclopropylene, cyclobutylene, etc.

The term “arylene” as used herein refers to a divalent mono-, bi- ortri-cyclic aromatic hydrocarbon portion having 6 to 20 ring-carbonatoms, preferably 6 to 12 ring-carbon atoms. The arylene groupinclusively refers to arylene groups additionally substituted with aspecific substituent, which will be described later. The aromaticportion includes carbon atoms only. The examples of the arylene maycomprise phenylene, etc.

The term “aralkylene” as used herein refers to a divalent portion of theabove-defined alkyl group in which at least one hydrogen atom issubstituted by an aryl group. The aralkylene group inclusively refers toaralkylene groups additionally substituted with a specific substituent,which will be described later. The examples of the aralkylene group maycomprise benzylene, etc.

The term “alkynylene” as used herein refers to a divalent linear orbranched hydrocarbon portion having 2 to 20 carbon atoms, preferably 2to 10 carbon atoms, more preferably 2 to 6 carbon atoms with at leastone carbon-carbon triple bond. The alkynylene group may form a bondingthrough carbon atoms including a carbon-carbon triple bond or throughsaturated carbon atoms. The alkynylene group inclusively refers toalkynylene groups additionally substituted with a specific substituent,which will be described later. The examples of the alkynylene group maycomprise ethynylene, propynylene, etc.

In the above description, the phrase “a substituent is substituted orunsubstituted” has an inclusive meaning that the substituent is or isn'tadditionally substituted with the substituent itself or another specificsubstituent. If not stated otherwise in this specification, the examplesof the substituent used as an additional substituent for eachsubstituent may include halogen, alkyl, alkenyl, alkynyl, haloalkyl,haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy,haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl,siloxy, or “a polar functional group comprising oxygen, nitrogen,phosphor, sulfur, silicon, or boron” as mentioned above.

The above-described cyclic olefin compound may be prepared by a typicalmethod of introducing a defined substituent, more specifically, aphotoreactive group of the formula 1a or 1b on a cyclic olefin such as anorbornene-based compound. The synthesis of the cyclic olefin compoundinvolves, for example, a condensation reaction of norbornene (alkyl)ol,such as norbornene methanol, and a carboxylic compound or the likehaving a photoreactive group of the formula 1a or 1b. Depending on thestructure and the type of the photoreactive group of the formula 1a or1b, any other different methods can be used to introduce thephotoreactive group and prepare the cyclic olefin compound.

On the other hand, the cyclic olefin compound can be used to prepare aphotoreactive polymer satisfying the characteristics of the embodimentof the present invention. The photoreactive polymer may comprise, as amain repeating unit, a cyclic olefin-based repeating unit represented bythe following formula 3a or 3b:

In the formulas 3a and 3b, independently, m is 50 to 5,000; and q, R1,R2, R3 and R4 are as defined in the formula 1.

This photoreactive polymer, which comprises a repeating unit derivedfrom the cyclic olefin compound, supports the formation of a large freevolume between adjacent photoreactive groups owing to the bulky aralkylstructure connected to the ends of the photoreactive groups via a linkerL. In the photoreactive polymer, consequently, the photoreactive groupsare relatively free to move (flow) or react in the secured large freevolume. Hence, the photoreactive polymer can exhibit better excellencesin photoreactivity, alignment rate, and photo-alignment, and have goodalignment stability so that it undergoes little change in thephoto-alignment characteristic in the presence of a change in theexposure conditions once a desired photo-alignment characteristic isacquired.

Accordingly, the photoreactive polymer makes it possible to realize thecharacteristics of the embodiment of the present invention and exhibitsexcellences in alignment rate and alignment stability.

The photoreactive polymer may further comprise a norbornene-basedrepeating unit of the formula 3a or 3b as a main repeating unit. Thenorbornene-based repeating unit is structurally rigid, and thephotoreactive polymer comprising the norbornene-based repeating unit hasa relatively high glass transition temperature Tg of about 300° C. orabove, preferably about 300 to 350° C., consequently with a higherthermal stability than the existing photoreactive polymers.

The definitions of the respective substituents bonded to thephotoreactive polymer are specified above in detail in regard to thecyclic olefin compound of the formula 1 and will not be described anymore.

The photoreactive polymer may comprise at least one repeating unitselected from the group consisting of the repeating units of the formula3a or 3b, or may be a copolymer further comprising another type ofrepeating unit. The examples of the repeating unit may comprise anyolefin-, acrylate- or cyclic-olefin-based repeating unit with or withouta bonding to cinnamate-, chalcone- or azo-based photoreactive groups.The exemplary repeating units are disclosed in Korean Patent Laid-openPublication No. 2010-0021751.

To prevent deterioration in good characteristics such as alignmentcharacteristic and alignment rate pertaining to the formula 3a or 3b,the photoreactive polymer may comprise the repeating unit of the formula3a or 3b in an amount of at least about 50 mol %, more specificallyabout 50 to 100 mol %, preferably at least about 70 mol %.

The repeating unit of the formula 3a or 3b constituting thephotoreactive polymer has a degree of polymerization in the range ofabout 50 to 5,000, preferably about 100 to 4,000, more preferably about1,000 to 3,000. The photoreactive polymer has a weight average molecularweight of 10,000 to 1000,000, preferably 20,000 to 500,000. Thephotoreactive polymer properly included in a coating composition forforming an alignment layer provides the coating composition with goodcoatability and the alignment layer formed from the coating compositionwith good liquid crystal alignment.

The photoreactive polymer may be endowed with photoreactivity uponexposure to a polarized radiation having a wavelength of about 150 to450 nm. For example, the photoreactive polymer can exhibit excellencesin photoreactivity, alignment characteristic, alignment rate, alignmentstability, or the like upon exposure to a polarized UV radiation havinga wavelength of about 200 to 400 nm, more specifically about 250 to 350nm. More specifically, the photoreactive polymer absorbs a polarized UVradiation in the wavelength range of about 270 to 340 nm to achieve theabove-mentioned characteristic value in regard to d(dichloricratio)/d(mJ/cm²), which guarantees excellences in alignment rate andalignment stability of the photoreactive polymer according to oneembodiment of the present invention.

The photoreactive polymer, when comprising a repeating unit of theformula 3a or 3b, may be prepared according to the following preparationmethods. One example of the preparation method may comprise conductingan addition polymerization reaction using a monomer represented by theformula 1 in the presence of a catalyst composition comprising aprecatalyst containing a transition metal in Group 10, and a cocatalystto form a repeating unit of the formula 3a:

In the formula 1, q, R1, R2, R3 and R4 are as defined in the formula 3a.

The polymerization reaction may be carried out at a temperature of 10 to200° C. The polymerization temperature below 10° C. lowers thepolymerization activity, while the temperature above 200° C. undesirablycauses a cleavage of the catalyst.

The cocatalyst comprises at least one selected from the group consistingof a first cocatalyst providing a Lewis base capable of forming a weakcoordinate bond with the metal of the precatalyst; and a secondcocatalyst providing a compound comprising a Group 15 electron donorligand. Preferably, the cocatalyst may be a catalyst mixture comprisingthe first cocatalyst providing a Lewis base, and optionally the secondcocatalyst providing a compound comprising a neutral Group 15 electrondonor ligand.

The catalyst mixture may comprise, based on one mole of the precatalyst,1 to 1,000 moles of the first cocatalyst and 1 to 1,000 moles of thesecond cocatalyst. The excessively low content of the first or secondcocatalyst causes a failure to provide the catalyst activity enough,while an excess of the first or second cocatalyst deteriorates thecatalyst activity.

The precatalyst comprising a Group 10 transition metal may be a compoundhaving a Lewis base functional group that is readily leaving from thecentral transition metal by the first cocatalyst providing a Lewis baseand participating in a Lewis acid-base reaction to help the centraltransition metal change into a catalyst active species. The examples ofthe precatalyst include allylpalladium chloride dimer([(Allyl)Pd(Cl)]₂), palladium(II) acetate ((CH₃CO₂)₂Pd), palladium(II)acetylacetonate ([CH₃COCH═C(O—)CH₃]₂Pd), NiBr(NP(CH₃)₃)₄,[PdCl(NB)O(CH₃)]₂, etc.

The first cocatalyst providing a Lewis base capable of forming a weakcoordinate bond with the metal of the precatalyst may be a compound thatreadily reacts with a Lewis base to leave vacancies in the transitionmetal and forms a weak coordinate bond with a transition metal compoundin order to stabilize the resultant transition metal; or a compoundproviding such a compound. The examples of the first cocatalyst mayinclude borane (e.g., B(C₆F₅)₃), borate (e.g., dimethylaniliniumtetrakis(pentafluorophenyl)borate), alkylaluminum (e.g.,methylaluminoxane (MAO) or Al(C₂H₅)₃), transition metal halide (e.g.,AgSbF₆), etc.

The examples of the second cocatalyst that provides a compoundcomprising a neutral Group 15 electron donor ligand may include alkylphosphine, cycloalkyl phosphine, or phenyl phosphine.

The first and second cocatalysts may be used separately, or usedtogether to form a single salt compound used as a compound foractivating the catalyst. For example, there may be a compound preparedas an ion pair of alkyl phosphine and a borane or borate compound.

The above-described method may be used to prepare a repeating unit ofthe formula 3a and a photoreactive polymer according to an embodimentcomprising the repeating unit. As for a photoreactive polymer furthercomprising an olefin-, cyclic-olefin- or acrylate-based repeating unit,typical preparation methods are used for forming each of thecorresponding repeating units, which is then copolymerized with therepeating unit of the formula 3a prepared by the above-described methodto form the photoreactive polymer.

On the other hand, a photoreactive polymer comprising a repeating unitof the formula 2a may be prepared according to another example of thepreparation method. The another exemplary preparation method comprisesperforming a ring-opening polymerization using a monomer of the formula1 in the presence of a catalyst composition comprising a precatalystcontaining a transition metal in Group 4, 6 or 8, and a cocatalyst toform a repeating unit of the formula 3b. Alternatively, thephotoreactive polymer comprising a repeating unit of the formula 3b maybe prepared by a method that comprises performing a ring-openingpolymerization using norbornene (alkyl)ol, such as norbornene methanol,as a norbornene monomer in the presence of a catalyst compositioncomprising a precatalyst containing a transition metal in Group 4, 6 or8, and a cocatalyst to form a ring-opened polymer with a 5-memberedring, and then introducing a photoreactive group on the ring-openedpolymer to complete the photoreactive polymer. Here, the introduction ofthe photoreactive group may be achieved using a condensation reaction ofthe ring-opened polymer with a carboxylate compound or an acyl chloridecompound having a photoreactive group of the formula 1a or 1b.

The ring-opening polymerization step may involve hydrogenation of thedouble bond of the norbornene ring included in the monomer of theformula 1 to open the norbornene ring, simultaneously beginning apolymerization reaction to prepare a repeating unit of the formula 3band a photoreactive polymer comprising the repeating unit.Alternatively, polymerization and ring-opening reactions may occur insequence to form the photoreactive polymer.

The ring-opening polymerization may be carried out in the presence of acatalyst composition, which comprises a precatalyst containing atransition metal in Group 4 (e.g., Ti, Zr, or Hf), Group 6 (e.g., Mo, orW) or Group 8 (e.g., Ru, or Os); a cocatalyst providing a Lewis basecapable of forming a weak coordinate bond with the metal of theprecatalyst; and optionally a neutral Group 15 or 16 activator forimproving the activity of the metal in the precatalyst. In the presenceof the catalyst composition, a linear alkene, such as 1-alkene,2-alkene, etc., controllable in molecular weight is added in an amountof 1 to 100 mol % with respect to the monomer to catalyze apolymerization reaction at 10 to 200° C. Then, a catalyst comprising atransition metal in Group 4 (e.g., Ti, or Zr) or Groups 8 to 10 (e.g.,Ru, Ni, or Pd) is added in an amount of 1 to 30 wt. % with respect tothe monomer to catalyze a hydrogenation reaction on the double bond ofthe norbornene ring at 10 to 250° C.

The excessively lower reaction temperature deteriorates thepolymerization activity, and the excessively higher reaction temperatureresults in an undesirable cleavage of the catalyst. The lowerhydrogenation temperature deteriorates the reaction activity, while theexcessively high hydrogenation temperature causes a cleavage of thecatalyst.

The catalyst composition comprises one mole of a precatalyst containinga transition metal in Group 4 (e.g., Ti, Zr, or Hf), Group 6 (e.g., Mo,or W) or Group 8 (e.g., Ru, or Os); 1 to 100,000 moles of a cocatalystproviding a Lewis base capable of forming a weak coordinate bond withthe metal of the precatalyst; and optionally 1 to 100 moles of anactivator comprising a neutral Group 15 or 16 element for improving theactivity of the metal of the precatalyst.

The cocatalyst content less than one mole causes a failure in activationof the catalyst, and the cocatalyst content greater than 100,000 molesdeteriorates the catalyst activity. The activator may be unnecessarydepending on the type of the precatalyst. The activator content lessthan one mole ends up with a failure of the catalyst activation, whilethe activator content greater than 100 moles results in a lowermolecular weight.

The hydrogenation reaction fails to occur when the content of thecatalyst comprising a transition metal of Group 4 (e.g., Ti, or Zr) orGroup 8, 9 or 10 (e.g., Ru, Ni, or Pd) for hydrogenation reaction isless than 1 wt. % with respect to the monomer. The catalyst contentgreater than 30 wt. % undesirably results in a discoloration of thepolymer.

The precatalyst comprising a transition metal in Group 4 (e.g., Ti, Zr,or Hf), Group 6 (e.g., Mo, or W) or Group 8 (e.g., Ru, or Os) may referto a transition metal compound, such as TiCl₄, WCl₆, MoCl₅, RuCl₃, orZrCl₄, having a functional group that is readily leaving from thecentral transition metal by the first cocatalyst providing a Lewis baseand participating in a Lewis acid-base reaction to help the centraltransition metal change into a catalyst active species.

The examples of the cocatalyst providing a Lewis base capable of forminga weak coordinate bond with the metal of the precatalyst may includeborane, such as B((C₆F₅)₃, or borate; or alkylaluminum, alkylaluminumhalide or aluminum halide, such as methylaluminoxane (MAO), Al(C₂H₅)₃,or Al(CH₃)Cl₂. Here, aluminum may be replaced by a substituent, such aslithium, magnesium, germanium, lead, zinc, tin, silicon, etc. Hence, thecocatalyst is a compound that readily reacts with a Lewis base toprovide vacancies in the transition metal and forms a weak coordinatebond with the transition metal compound in order to stabilize theproduced transition metal; or a compound providing such a compound.

Depending on the type of the precatalyst, a polymerization activator isrequired or not. The examples of the activator comprising a neutralelement in Group 15 or 16 may include water, methanol, ethanol,isopropyl alcohol, benzylalcohol, phenol, ethyl mercaptan,2-chloroethanol, trimethylamine, triethylamine, pyridine, ethyleneoxide, benzoyl peroxide, t-butyl peroxide, or the like.

The catalyst comprising a transition metal in Group 4 (e.g., Ti, or Zr)or Group 8, 9 or 10 (e.g., Ru, Ni, or Pd) used for hydrogenationreaction may be prepared as a homogeneous form miscible with a solvent,or as a metal complex catalyst impregnated on a particulate support.Preferably, the examples of the particulate support include silica,titania, silica/chromia, silica/chromia/titania, silica/alumina,aluminum phosphate gel, silanized silica, silica hydrogel,montmorillonite clay, or zeolite.

The above-described method is used to prepare the repeating unit of theformula 3b and the photoreactive polymer of the embodiment comprisingthe repeating unit. As for the photoreactive polymer that furthercomprises an olefin-, cyclic-olefin- or acrylate-based repeating unit,the respective repeating units are first formed through thecorresponding preparation methods and then copolymerized with arepeating unit of the formula 3b prepared by the above-described methodto form the photoreactive polymer.

In accordance with still another embodiment of the invention, there isprovided an alignment layer comprising the above-described photoreactivepolymer. The alignment layer may be of a thin film form or an alignmentlayer form.

The alignment layer may be prepared using known preparation methods withconstituent components known to those skilled in the art, excepting thata photo-aligned polymer is used as the photoreactive polymer.

For example, the alignment layer is prepared by mixing the photoreactivepolymer with a binder resin and a photo-initiator, dissolving themixture in an organic solvent to obtain a coating composition, applyingthe coating composition on a base, and then curing the coatingcomposition by UV exposure.

Here, the binder resin may be an acrylate-based resin, morespecifically, pentaerythritol triarylate, dipentaerythritolhexaacrylate, trimethylolpropane triacrylate, tris(2-acryloyloxyethyl)isocyanurate, etc.

The photo-initiator may be any typical photo-initiator known to beapplicable to alignment layers without any limitations, such as, forexample, Irgacure 907 or Irgacure 819.

The examples of the organic solvent may include toluene, anisole,chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propyleneglycol, methyl ether, acetate, etc. Other organic solvent may also beused without any limitations, because the photoreactive norbornene-basedcopolymer has a good solubility in various organic solvents.

In the coating composition, the content of the solid componentscomprising the binder resin and the photo-initiator may be in the rangeof 1 to 15 wt. %, preferably 10 to 15 wt. % to cast the alignment layerinto films, or 1 to 5 wt. % to cast the alignment layer into thin films.

The alignment layer may be formed, for example, on a support as shown inFIG. 1, or under liquid crystals to achieve liquid crystal alignment.Here, the base may be a cyclic polymer base, an acryl polymer base, or acellulose polymer base. The coating composition is applied on the baseby different methods, such as bar coating, spin coating, blade coating,etc. and then cured under UV exposure to form an alignment layer.

The UV curing causes photo-alignment, in which step a polarized UVradiation having a wavelength of about 150 to 450 nm is applied to bringabout alignment. Here, the exposure intensity of the radiation is about10 mJ/cm² to 10 J/cm², preferably, about 20 mJ/cm² to 2.5 J/c m².

The UV radiation as used herein may be any UV radiations polarized bypassing through or being reflected from (a) a polarizer using adielectric anisotropic coating on the surface of a transparent substratesuch as quartz glass, soda-lime glass, soda-lime-free glass, or thelike; (b) a polarizer with fine aluminum or other metallic wires; or (c)a Brewster polarizer using reflection from quartz glass.

The substrate temperature during UV exposure is preferably the roomtemperature. Under circumstances, the substrate may be heated at 100° C.or below during UV exposure. Preferably, the final layer thus obtainedfrom the above-described steps has a thickness of about 30 to 1,000 μm.

The above-described method is adopted to form an alignment layer. Theuse of the photoreactive polymer in the alignment layer enables thealignment layer to have good interactions with liquid crystal molecules,achieving effective photo-alignment. Also, the photoreactive polymerprovides the alignment layer with desired alignment characteristicsuniform and stable and enables a preparation of the alignment layer withmore efficiency due to its high alignment rate.

In accordance with still further another embodiment of the invention,there is provided a display device comprising the alignment layer. Thedisplay device may be a liquid crystal display device comprising thealignment layer for liquid crystal alignment; or a stereoscopic imagingdisplay device included in optical films or filters to createstereoscopic images. The constituent components of the display deviceare the same as those of a typical display device, excepting that thephotoreactive polymer and the alignment layer are included, and will notbe described any more in further detail.

In the following are set forth preferred examples of the invention forbetter understanding of the invention. It is to be understood that theexamples are only for illustrative purposes and are not intended tolimit the scope of the invention.

COMPARATIVE EXAMPLE 1 Polyvinyl cinnamate

Polyvinyl cinnamate was purchased from Aldrich Chemicals.

COMPARATIVE EXAMPLE 2 Poly(cinnamate-ethyl-methacrylate)

Hydroxyl ethyl methacrylate (10 g), cinnamoyl chloride (1 eq), andtriethylamine (3 eq) were dissolved in THF and stirred at 10° C. for 16hours. After completion of the reaction, the reaction mixture wasfiltered to eliminate salts and extracted with EA/H₂O. Removed of theorganic solvent, the residual was purified by column chromatography(EA/hexane (2/1)) to obtain a product (yield: 82%).

The product (5 g) and AlBN (0.02 eq) were put in toluene and stirred at70° C. for 15 hours. Then, the polymerization solution was added toethanol to precipitate a polymer product (Mw=46 k, PDI=2.38, yield=62%).

EXAMPLE 1 Preparation of 4-benzyloxy-cinnamate-5-norbornene(cyclicolefin compound)

4-Benzyloy-benzaldehyde (10 g, 47 mmol), malonic acid (2 eq.) andpiperidine (0.1 eq.) were dissolved in pyridine (5 eq.) and stirred at80° C. for 5 hours. After completion of the reaction, the reactionmixture was cooled down to the room temperature and neutralized with 3MHCl. The white solid thus obtained was filtered out and dried in avacuum oven to yield 4-benzyloxy-cinnamic acid.

The 4-benzyloxy-cinnamic acid (5 g, 19.7 mmol), norbornene-5-ol (19mmol) and Zr(AcAc) (0.2 mol. %) were put in xylene and stirred at 190°C. for 24 hours. Then, the reaction mixture was washed with 1M HCl and1M NaHCO3 aqueous solutions and removed of the solvent to obtain ayellowish solid, 4-benzyloxy-cinnamate-5-norbornene.

NMR(CDCl₃(500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.87(1, m)2.56(1, m) 2.93(1, s) 5.11(2, s) 5.98˜6.19(2, m) 6.36(1, d) 7.3˜7.5(9,m) 7.63(2, d).

EXAMPLE 2 Preparation of 4-benzyloxy-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-benzyloxy-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.87(1,m) 2.47(1, m) 2.93(1, s) 3.8˜4.25(2, m) 5.11(2, s) 5.98˜6.19(2, m)6.36(1, d) 7.3˜7.5(9, m) 7.63(2, d).

EXAMPLE 3 Preparation of 4-benzyloxy-cinnamate-5-ethyl norbornene(cyclicolefin compound)

The procedures were performed in the same manner as described in Example1, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-benzyloxy-cinnamate-5-ethyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.33˜1.6(3, m)1.8(1, m) 2.43(1, m) 2.90(1, s) 3.3˜3.9(2, m) 5.11(2, s) 5.95˜6.17(2, m)6.36(1, d) 7.3˜7.5(9, m) 7.63(2, d).

EXAMPLE 4 Preparation of4-(4-fluoro-benzyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-fluoro-benzyloxy)-benzaldehyde was used insteadof 4-benzyloxy-benzaldehyde to prepare4-(4-fluoro-benzyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 5.05(2, s) 5.97˜6.11(2, m) 6.30(1, d) 6.97(2,d)7.1(2, m) 7.4(2, m) 7.49(2, d) 7.65(1, s).

EXAMPLE 5 Preparation of 4-(4-fluoro-benzyloxy)-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example4, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-fluoro-benzyloxy)-cinnamate-5-methylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.47(1, m) 2.93(1, s) 5.05(2, s) 5.97˜6.11(2, m) 6.30(1, d) 6.97(2,d)7.1(2, m) 7.4(2, m) 7.49(2, d) 7.65(1, s).

EXAMPLE 6 Preparation of 4-(4-fluoro-benzyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example4, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-fluoro-benzyloxy)-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.36˜1.6(3, m)1.86(1, m) 2.45(1, m) 2.91(1, s) 3.32˜3.96(2, m) 5.05(2, s) 5.97˜6.11(2,m) 6.30(1, d) 6.97(2,d) 7.1(2, m) 7.4(2, m) 7.49(2, d) 7.65(1, s).

EXAMPLE 7 Preparation of4-(4-methyl-benzyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-methyl-benzyloxy)-benzaldehyde was used insteadof 4-benzyloxy-benzaldehyde to prepare4-(4-methyl-benzyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.21˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.37(3, s) 2.67(1, m) 2.93(1, s) 5.05(2, s) 5.97˜6.11(2, m) 6.30(1,d) 6.97(2, m) 7.1(2, m) 7.4(2, m) 7.45(2, d) 7.65(1, s).

EXAMPLE 8 Preparation of 4-(4-methyl-benzyloxy)-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example7, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-methyl-benzyloxy)-cinnamate-5-methylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.37(3, s) 2.47(1, m) 2.93(1, s) 3.74˜4.28(2, m) 5.05(2, s)5.97˜6.11(2, m) 6.30(1, d) 6.97(2, d) 7.1(2, m) 7.4(2, m) 7.47(2, d)7.65(1, s).

EXAMPLE 9 Preparation of 4-(4-methyl-benzyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example7, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-methyl-benzyloxy)-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.35˜1.6(3, m)1.86(1, m) 2.37(3, s) 2.45(1, m) 2.91(1, s) 3.33˜3.96(2, m) 5.05(2, s)5.97˜6.11(2, m) 6.30(1, d) 6.97(2, d) 7.1(2, m) 7.4(2, m) 7.49(2, d)7.65(1, s).

EXAMPLE 10 Preparation of4-(4-methoxy-benzyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-methoxy-benzyloxy)-benzaldehyde was used insteadof 4-benzyloxy-benzaldehyde to prepare4-(4-methoxy-benzyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.20˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 4.44(3, s) 5.05(2, s) 5.98˜6.11(2, m) 6.30(1,d) 7.01(2, d) 7.16(2, m) 7.44(2, m) 7.51(2, d) 7.65(1, s).

EXAMPLE 11 Preparation of 4-(4-methoxy-benzyloxy)-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example10, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-methoxy-benzyloxy)-cinnamate-5-methylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.47(1, m) 2.93(1, s) 3.75˜4.3(2, m) 5.05(2, s) 5.97˜6.11(2, m)6.30(1, d) 6.97(2, d) 7.01(2, d) 7.16(2, m) 7.44(2, m) 7.51(2, d)7.65(1, s).

EXAMPLE 12 Preparation of 4-(4-methoxy-benzyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example10, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-methoxy-benzyloxy)-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.33˜1.57(3, m)1.86(1, m) 2.45(1, m) 2.92(1, s) 3.32˜3.96(2, m) 5.05(2, s) 5.97˜6.11(2,m) 6.30(1, d) 7.01(2, d) 7.16(2, m) 7.44(2, m) 7.51(2, d) 7.65(1, s).

EXAMPLE 13 Preparation of4-(2-naphthalene-methyloxy)-cinnamate-5-norbornene(cyclic olefincompound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(2-naphthalene-methyloxy)-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare4-(2-naphthalene-methyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.64(1, m) 2.93(1, s) 5.28(2, s) 5.97˜6.11(2, m) 6.31(1, d) 6.63(2,d) 7.5(6, m) 7.9(4, m).

EXAMPLE 14 Preparation of 4-(2-naphthalene-methyloxy)-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example13, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare4-(2-naphthalene-methyloxy)-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.48(1, m) 2.91(1, s) 3.75˜4.3(2, m) 5.28(2, s) 5.97˜6.11(2, m)6.31(1, d) 6.63(2, d) 7.5(6, m) 7.9(4, m).

EXAMPLE 15 Preparation of 4-(2-naphthalene-methyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example13, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(2-naphthalene-methyloxy)-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.21˜1.27(2, m) 1.37˜1.6(3, m)1.86(1, m) 2.45(1, m) 2.90(1, s) 3.62˜4.05(2, m) 5.05(2, s) 5.97˜6.11(2,m) 6.31(1, d) 6.63(2, d) 7.5(6, m) 7.9(4, m).

EXAMPLE 16 Preparation of 4-(4-methylketonebenzyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-methylketone benzyloxy)-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare 4-(4-methyl ketonebenzyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 3.66(3, s) 5.05(2, s) 5.97˜6.11(2, m) 6.27(1,d) 7.0(2, d) 7.1(2, m) 7.4(2, m) 7.50(2, d) 7.65(1, s).

EXAMPLE 17 Preparation of 4-(4-methylketonebenzyloxy)-cinnamate-5-methyl norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example16, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-methylketonebenzyloxy)-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.87(1,m) 2.47(1, m) 2.93(1, s) 3.66(3, s) 3.8˜4.25(2, m) 5.05(2, s)5.97˜6.11(2, m) 6.27(1, d) 7.0(2, d) 7.1(2, m) 7.4(2, m) 7.50(2, d)7.65(1, s).

EXAMPLE 18 Preparation of 4-(4-methylketone benzyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example16, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-methylketonebenzyloxy)-cinnamate-5-ethyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.24˜1.29(2, m) 1.33˜1.6(3, m)1.8(1, m) 2.43(1, m) 2.90(1, s) 3.66(3, s) 3.8˜4.25(2, m) 5.05(2, s)5.97˜6.11(2, m) 6.27(1, d) 7.0(2, d) 7.1(2, m) 7.4(2, m) 7.50(2, d)7.65(1, s).

EXAMPLE 19 Preparation of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(1-phenyl perfluoroheptyloxy)-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.87(1,m) 2.56(1, m) 2.93(1, s) 5.10(2, s) 5.96˜6.16(2, m) 6.55(1, d)7.4˜7.55(5, m) 7.65(2, d) 7.68(4, m).

EXAMPLE 20 Preparation of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-methyl norbornene(cyclic olefincompound)

The procedures were performed in the same manner as described in Example19, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.87(1,m) 2.56(1, m) 2.93(1, s) 3.75˜4.3(2, m) 5.10(2, s) 5.96˜6.16(2, m)6.55(1, d) 7.4˜7.55(5, m) 7.65(2, d) 7.68(4, m).

EXAMPLE 21 Preparation of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-ethyl norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example19, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-ethyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.34˜1.59(3, m)1.86(1, m) 2.56(1, m) 2.92(1, s) 3.31˜3.96(2, m) 5.10(2, s) 5.96˜6.16(2,m) 6.55(1, d) 7.4˜7.55(5, m) 7.65(2, d) 7.68(4, m).

EXAMPLE 22 Preparation of4-(4-benzyloxy)-benzyloxy-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-benzyloxy)-benzyloxy-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare4-(4-benzyloxy)-benzyloxy-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 5.16(4, s) 5.97˜6.11(2, m) 6.30(1, d)6.99˜7.15(8,d) 7.4˜7.51(5, d) 7.61(1, s).

EXAMPLE 23 Preparation of 4-(4-benzyloxy)-benzyloxy-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example22, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-benzyloxy)-benzyloxy-cinnamate-5-methylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.47(1, m) 2.93(1, s) 3.75˜4.3(2, m) 5.16(4, s) 5.97˜6.11(2, m)6.30(1, d) 6.99˜7.15(8,d) 7.4˜7.51(5, d) 7.61(1, s).

EXAMPLE 24 Preparation of 4-(4-benzyloxy)-benzyloxy-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example22, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-benzyloxy)-benzyloxy-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.36˜1.6(3, m)1.86(1, m) 2.45(1, m) 2.91(1, s) 3.32˜3.96(2, m) 5.16(4, s) 5.97˜6.11(2,m) 6.30(1, d) 6.99˜7.15(8,d) 7.4˜7.51(5, d) 7.61(1, s).

EXAMPLE 25 Preparation of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-norbornene(cyclic olefincompound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-fluoro-phenyloxy)-benzyloxy-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.55(1, m) 2.91(1, s) 5.08(4, s) 5.91˜6.11(2, m) 6.30(1, d) 6.97(2,d)7.20(2, m) 7.31˜7.63(8, m) 7.68(1, s) 7.84(2, d).

EXAMPLE 26 Preparation of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-methyl norbornene(cyclicolefin compound)

The procedures were performed in the same manner as described in Example25, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.55(1, m) 2.92(1, s) 3.75˜4.3(2, m) 5.08(4, s) 5.91˜6.11(2, m)6.30(1, d) 6.97(2,d) 7.20(2, m) 7.31˜7.63(8, m) 7.68(1, s) 7.84(2, d).

EXAMPLE 27 Preparation of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-ethyl norbornene(cyclicolefin compound)

The procedures were performed in the same manner as described in Example25, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-ethyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.36˜1.6(3, m)1.86(1, m) 2.55(1, m) 2.92(1, s) 3.32˜3.96(2, m) 5.08(4, s) 5.91˜6.11(2,m) 6.30(1, d) 6.97(2,d) 7.20(2, m) 7.31˜7.63(8, m) 7.68(1, s) 7.84(2,d).

EXAMPLE 28 Preparation of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-norbornene(cyclic olefincompound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-trifluoromethyl)-benzyloxy-benzaldehyde was usedinstead of 4-benzyloxy-benzaldehyde to prepare4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 5.05(2, s) 5.97˜6.11(2, m) 6.30(1, d)7.11˜7.25(4, m) 7.4(2, m) 7.60˜7.68(3, m).

EXAMPLE 29 Preparation of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-methyl norbornene(cyclicolefin compound)

The procedures were performed in the same manner as described in Example28, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-methyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.47(1, m) 2.93(1, s) 3.74˜4.28(2, m) 5.05(2, s) 5.97˜6.11(2, m)6.30(1, d) 7.11˜7.25(4, m) 7.4(2, m) 7.60˜7.68(3, m).

EXAMPLE 30 Preparation of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-ethyl norbornene(cyclicolefin compound)

The procedures were performed in the same manner as described in Example28, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-ethyl norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.36˜1.6(3, m)1.86(1, m) 2.45(1, m) 2.91(1, s) 3.32˜3.96(2, m) 5.05(2, s) 5.97˜6.11(2,m) 6.30(1, d) 7.11˜7.25(4, m) 7.4(2, m) 7.60˜7.68(3, m).

EXAMPLE 31 Preparation of4-(4-bromo-benzyloxy)-cinnamate-5-norbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example1, excepting that 4-(4-bromo-benzyloxy)-benzaldehyde was used instead of4-benzyloxy-benzaldehyde to prepare4-(4-bromo-benzyloxy)-cinnamate-5-norbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.67(1, m) 2.93(1, s) 5.05(2, s) 5.97˜6.11(2, m) 6.30(1, d) 6.97(2,d)7.1(2, m) 7.30(2, m) 7.45(2, d) 7.61(1, s).

EXAMPLE 32 Preparation of 4-(4-bromo-benzyloxy)-cinnamate-5-methylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example31, excepting that norbornene-5-methanol was used instead ofnorbornene-5-ol to prepare 4-(4-bromo-benzyloxy)-cinnamate-5-methylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.47(1,d) 1.88(1,m) 2.47(1, m) 2.93(1, s) 3.75˜4.3(2, m) 5.05(2, s) 5.97˜6.11(2, m)6.30(1, d) 6.97(2,d) 7.1(2, m) 7.30(2, m) 7.45(2, d) 7.61(1, s).

EXAMPLE 33 Preparation of 4-(4-bromo-benzyloxy)-cinnamate-5-ethylnorbornene(cyclic olefin compound)

The procedures were performed in the same manner as described in Example31, excepting that norbornene-5-ethanol was used instead ofnorbornene-5-ol to prepare 4-(4-bromo-benzyloxy)-cinnamate-5-ethylnorbornene.

NMR(CDCl₃ (500 MHz), ppm): 0.6(1, m) 1.22˜1.27(2, m) 1.36˜1.6(3, m)1.86(1, m) 2.45(1, m) 2.91(1, s) 3.32˜3.96(2, m) 5.05(2, s) 5.97˜6.11(2,m) 6.30(1, d) 6.97(2,d) 7.1(2, m) 7.30(2, m) 7.45(2, d) 7.61(1, s).

EXAMPLE 34 Polymerization of 4-benzyloxy-cinnamate-5-norbornene

In a 250 ml Schlenk flask were placed 4-benzyloxy-cinnamate-5-norbornene(50 mmol) of Example 1 as a monomer, and purified toluene (400 wt. %) asa solvent. 1-octene (10 mol. %) was also added. Under agitation, themixture was heated to 90° C. To the flask were added Pd(OAc)₂ (16 μmol)and tricyclohexylphosphine (32 μmol) in 1 ml of dichloromethane as acatalyst, and dimethylanilinium tetrakiss(pentafluorophenyl)borate (32μmol) as a cocatalyst. The mixture was stirred at 90° C. for 16 hours tobring about a reaction.

After completion of the reaction, the reactant mixture was put in anexcess of ethanol to obtain a white polymer precipitate. The precipitatewas filtered out through a glass funnel to collect a polymer, which wasthen dried in a vacuum oven at 60° C. for 24 hours to yield a finalpolymer product (Mw=198 k, PDI=3.22, yield=68%).

EXAMPLE 35 Polymerization of 4-benzyloxy-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-benzyloxy-cinnamate-5-methyl norbornene (50 mmol)of Example 2 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=162 k, PDI=3.16, yield=81%).

EXAMPLE 36 Polymerization of 4-benzyloxy-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) ofExample 3 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=159 k, PDI=4.10, yield=80%).

EXAMPLE 37 Polymerization of4-(4-fluoro-benzyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 4 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=121 k, PDI=3.52, yield=62%).

EXAMPLE 38 Polymerization of 4-(4-fluoro-benzyloxy)-cinnamate-5-methylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 5 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=135 k, PDI=2.94, yield=82%).

EXAMPLE 39 Polymerization of 4-(4-fluoro-benzyloxy)-cinnamate-5-ethylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 6 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=144 k, PDI=4.03, yield=74%).

EXAMPLE 40 Polymerization of4-(4-methyl-benzyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 7 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=111 k, PDI=3.56, yield=58%).

EXAMPLE 41 Polymerization of 4-(4-methyl-benzyloxy)-cinnamate-5-methylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 8 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=134 k, PDI=3.71, yield=75%).

EXAMPLE 42 Polymerization of 4-(4-methyl-benzyloxy)-cinnamate-5-ethylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 9 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=130 k, PDI=4.00, yield=71%).

EXAMPLE 43 Polymerization of4-(4-methoxy-benzyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 10 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=146 k, PDI=3.42, yield=74%).

EXAMPLE 44 Polymerization of 4-(4-methoxy-benzyloxy)-cinnamate-5-methylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 11 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=144 k, PDI=3.04, yield=79%).

EXAMPLE 45 Polymerization of 4-(4-methoxy-benzyloxy)-cinnamate-5-ethylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 12 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=123 k, PDI=3.69, yield=71%).

EXAMPLE 46 Polymerization of4-(2-naphthalene-methyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-norbornene(50 mmol) of Example 13 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=91 k, PDI=4.01, yield=54%).

EXAMPLE 47 Polymerization of4-(2-naphthalene-methyloxy)-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 14 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=83 k, PDI=3.97, yield=61%).

EXAMPLE 48 Polymerization of4-(2-naphthalene-methyloxy)-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 15 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=102 k, PDI=3.72, yield=43%).

EXAMPLE 49 Polymerization of 4-(4-methyl ketonebenzyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-norbornene(50 mmol) of Example 16 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=109 k, PDI=4.23, yield=47%).

EXAMPLE 50 Polymerization of 4-(4-methylketonebenzyloxy)-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 17 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=111 k, PDI=4.21, yield=51%).

EXAMPLE 51 Polymerization of 4-(4-methylketonebenzyloxy)-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 18 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=87 k, PDI=3.32, yield=43%).

EXAMPLE 52 Polymerization of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-norbornene (50 mmol) of Example 19 wasused as a monomer instead of 4-benzyloxy-cinnamate-5-norbornene ofExample 1 to obtain a polymer product (Mw=116 k, PDI=3.09, yield=57%).

EXAMPLE 53 Polymerization of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(1-phenyl perfluoroheptyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 20 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=105 k, PDI=3.88, yield=69%).

EXAMPLE 54 Polymerization of 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(1-phenyl perfluoroheptyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 21 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=87 k, PDI=4.62, yield=51%).

EXAMPLE 55 Polymerization of4-(4-benzyloxy)-benzyloxy-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-norbornene (50mmol) of Example 22 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=137 k, PDI=3.19, yield=68%).

EXAMPLE 56 Polymerization of4-(4-benzyloxy)-benzyloxy-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 23 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=121 k, PDI=3.52, yield=74%).

EXAMPLE 57 Polymerization of 4-(4-benzyloxy)-benzyloxy-cinnamate-5-ethylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 24 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=130 k, PDI=4.67, yield=63%).

EXAMPLE 58 Polymerization of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-norbornene (50 mmol) ofExample 25 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=154 k, PDI=3.22, yield=72%).

EXAMPLE 59 Polymerization of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 26 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=148 k, PDI=3.61, yield=73%).

EXAMPLE 60 Polymerization of4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 27 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=116 k, PDI=4.17, yield=68%).

EXAMPLE 61 Polymerization of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-norbornene (50 mmol) ofExample 28 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=133 k, PDI=3.10, yield=44%).

EXAMPLE 62 Polymerization of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-methyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 29 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=121 k, PDI=3.38, yield=48%).

EXAMPLE 63 Polymerization of4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-ethyl norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 30 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=127 k, PDI=3.32, yield=41%).

EXAMPLE 64 Polymerization of4-(4-bromo-benzyloxy)-cinnamate-5-norbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 31 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=168 k, PDI=3.06, yield=74%).

EXAMPLE 65 Polymerization of 4-(4-bromo-benzyloxy)-cinnamate-5-methylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 32 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=160 k, PDI=3.24, yield=83%).

EXAMPLE 66 Polymerization of 4-(4-bromo-benzyloxy)-cinnamate-5-ethylnorbornene

The procedures were performed in the same manner as described in Example34, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 33 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to obtain a polymerproduct (Mw=146 k, PDI=3.52, yield=72%).

EXAMPLE 67 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-Benzyloxy-Cinnamate-5-Norbornene

In a 250 ml Schlenk flask in the Ar atmosphere were placed4-benzyloxy-cinnamate-5-norbornene (50 mmol) and then purified toluene(600 wt. %) as a solvent. With the flask maintained at a polymerizationtemperature of 80° C., triethyl aluminum (1 mmol) was added as acocatalyst. Subsequently, to the flask was added 1 ml (WCl₈: 0.01 mmol,ethanol: 0.03 mmol) of a 0.01M (mol/L) toluene solution containing amixture of tungsten hexachloride (WCl₈) and ethanol at a mixing ratio of1:3. Finally, 1-octene (15 mol. %) was added as a molecular weightmodifier to the flask, which was then stirred at 80° C. for 18 hours tobring about a reaction. After completion of the reaction, a small amountof ethyl vinyl ether as a polymerization inhibitor was added dropwise tothe polymerization solution, and the flask was stirred for 5 minutes.

With the polymerization solution transferred to a 300 mL high-pressurereactor, 0.06 ml of triethyl aluminum (TEA) was added to the solution.Subsequently, 0.50 g of grace raney nickel (slurry phase in water) wasadded, and the solution was stirred at 150° C. for 2 hours under thehydrogen pressure maintained at 80 atm to bring about a reaction. Aftercompletion of the reaction, the polymerization solution was addeddropwise to acetone to cause precipitation. The precipitate thusobtained was filtered out and dried in a vacuum oven at 70° C. for 15hours, thereby obtaining a ring-opened hydrogenated polymer of4-benzyloxy-cinnamate-5-norbornene (Mw=83 k, PDI=4.92, yield=88%).

EXAMPLE 68 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-Benzyloxy-Cinnamate-5-MethylNorbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-benzyloxy-cinnamate-5-methyl norbornene (50 mmol)of Example 2 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=87k, PDI=4.22, yield=87%).

EXAMPLE 69 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-Benzyloxy-Cinnamate-5-EthylNorbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) ofExample 3 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=71k, PDI=4.18, yield=80%).

EXAMPLE 70 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Benzyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 4 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=90k, PDI=3.40, yield=71%).

EXAMPLE 71 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Benzyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 5 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=87k, PDI=3.98, yield=76%).

EXAMPLE 72 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Benzyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-fluoro-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 6 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=68k, PDI=3.51, yield=74%).

EXAMPLE 73 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methyl-Benzyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 7 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=69k, PDI=4.13, yield=77%).

EXAMPLE 74 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methyl-Benzyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 8 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=81k, PDI=3.49, yield=84%).

EXAMPLE 75 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methyl-Benzyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methyl-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 9 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=55k, PDI=5.37, yield=68%).

EXAMPLE 76 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methoxy-Benzyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 10 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=88k, PDI=3.56, yield=84%).

EXAMPLE 77 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methoxy-Benzyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 11 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=81k, PDI=3.14, yield=80%).

EXAMPLE 78 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Methoxy-Benzyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methoxy-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 12 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=84k, PDI=3.90, yield=73%).

EXAMPLE 79 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(2-Naphthalene-Methyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-norbornene(50 mmol) of Example 13 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=49k, PDI=4.53, yield=55%).

EXAMPLE 80 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(2-Naphthalene-Methyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 14 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=53k, PDI=3.91, yield=51%).

EXAMPLE 81 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(2-Naphthalene-Methyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(2-naphthalene-methyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 15 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=59k, PDI=3.99, yield=54%).

EXAMPLE 82 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(4-MethylketoneBenzyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-norbornene(50 mmol) of Example 16 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=93k, PDI=3.49, yield=88%).

EXAMPLE 83 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(4-MethylketoneBenzyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 17 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=85k, PDI=4.26, yield=81%).

EXAMPLE 84 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(4-MethylketoneBenzyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-methylketone benzyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 18 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=94k, PDI=4.56, yield=71%).

EXAMPLE 85 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(1-PhenylPerfluoroheptyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(1-phenylperfluoroheptyloxy)-cinnamate-5-norbornene (50 mmol) of Example 19 wasused as a monomer instead of 4-benzyloxy-cinnamate-5-norbornene ofExample 1 to form a polymer (Mw=42 k, PDI=4.37, yield=54%).

EXAMPLE 86 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(1-PhenylPerfluoroheptyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(1-phenyl perfluoroheptyloxy)-cinnamate-5-methylnorbornene (50 mmol) of Example 20 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=45k, PDI=3.92, yield=52%).

EXAMPLE 87 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of 4-(1-PhenylPerfluoroheptyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(1-phenyl perfluoroheptyloxy)-cinnamate-5-ethylnorbornene (50 mmol) of Example 21 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=44k, PDI=4.52, yield=43%).

EXAMPLE 88 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Benzyloxy)-Benzyloxy-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-norbornene (50mmol) of Example 22 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=82k, PDI=3.44, yield=70%).

EXAMPLE 89 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Benzyloxy)-Benzyloxy-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 23 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=76k, PDI=3.67, yield=73%).

EXAMPLE 90 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Benzyloxy)-Benzyloxy-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-benzyloxy)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 24 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=68k, PDI=4.81, yield=65%).

EXAMPLE 91 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Phenyloxy)-Benzyloxy-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-norbornene (50 mmol) ofExample 25 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=51k, PDI=4.72, yield=41%).

EXAMPLE 92 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Phenyloxy)-Benzyloxy-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 26 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=55k, PDI=4.13, yield=47%).

EXAMPLE 93 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Fluoro-Phenyloxy)-Benzyloxy-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-fluoro-phenyloxy)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 27 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=49k, PDI=4.11, yield=42%).

EXAMPLE 94 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Trifluoromethyl)-Benzyloxy-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-norbornene (50 mmol) ofExample 28 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=53k, PDI=3.01, yield=56%).

EXAMPLE 95 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Trifluoromethyl)-Benzyloxy-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-methylnorbornene (50 mmol) of Example 29 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=72k, PDI=3.95, yield=55%).

EXAMPLE 96 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Trifluoromethyl)-Benzyloxy-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-trifluoromethyl)-benzyloxy-cinnamate-5-ethylnorbornene (50 mmol) of Example 30 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=59k, PDI=3.72, yield=50%).

EXAMPLE 97 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Bromo-Benzyloxy)-Cinnamate-5-Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-norbornene (50mmol) of Example 31 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=97k, PDI=3.14, yield=80%).

EXAMPLE 98 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Bromo-Benzyloxy)-Cinnamate-5-Methyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-methyl norbornene(50 mmol) of Example 32 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=93k, PDI=3.28, yield=83%).

EXAMPLE 99 Polymer Preparation Using Ring-Opening MethathesisPolymerization and Hydrogenation of4-(4-Bromo-Benzyloxy)-Cinnamate-5-Ethyl Norbornene

The procedures were performed in the same manner as described in Example67, excepting that 4-(4-bromo-benzyloxy)-cinnamate-5-ethyl norbornene(50 mmol) of Example 33 was used as a monomer instead of4-benzyloxy-cinnamate-5-norbornene of Example 1 to form a polymer (Mw=88k, PDI=3.93, yield=81%).

EXPERIMENTAL EXAMPLE 1 Fabrication of Liquid Crystal Film and Evaluationof Alignment Characteristics

Based on the total weight of the solution, 2 to 3 wt. % of eachphotoreactive polymer of Examples and Comparative Examples, 0.5 to 1.0wt. % of a binder (i.e., an acryl-based binder, such as PETA, DPHA ortriacryl isocyanurate), and 0.05 to 1 wt. % of a photo-initiator(Irgacure 907, Ciba) were dissolved in a toluene solvent, and theresultant solution was put dropwise on a glass substrate or a polymerfilm (e.g., COC, COP, or TAC) to conduct a bar coating. The bar-coatedfilm was dried at 80° C. for 2 min. and exposed to a polarized UVradiation to form an alignment layer through photo-alignment. A-plateliquid crystal (25 wt. % in toluene) was put dropwise on the alignmentlayer for bar coating, dried at 60° C. for 2 min. and exposed to 20 mJof UV radiation for liquid crystal curing.

The respective alignment layers prepared from the photoreactive polymersof Examples 34, 38 and 50, and Comparative Examples 1 and 2 weremeasured in regard to a change of d(dichloric ratio)/d(mJ/cm²) asfollows.

The photoreactive polymers were exposed to a polarized UV radiationhaving a wavelength of about 150 to 450 nm so that the exposure dose onthe photoreactive polymer was 20 mJ/cm² per second. The exposure timewas adjusted to control the total exposure dose on the polymer in thealignment layer. The dichloric ratio based on the exposure time and thetotal exposure dose was then measured. For measurement of the dichloricratio, polarizers were arranged in a UV-vis spectrometer to determineabsorbance A(parallel) and absorbance A(perpendicular) and calculate thedichloric ratio according to an equation given byDR=(A(∥)−A(⊥))/(A(∥)+A(⊥)), where the reference wavelength was 310 nm.From the dichloric ratio measured by the total exposure dose, avariation in the dichloric ratio per unit exposure dose as given byd(dichloric ratio)/d(mJ/cm²) was calculated according to the totalexposure dose. The results are presented in FIGS. 2 and 3.

More specifically, the change of d(dichloric ratio)/d(mJ/cm²) that is avariation in the dichloric ratio per unit exposure dose (mJ/cm²) wasmeasured based on the total exposure dose 250 mJ/cm² or less and plottedin a graph as shown in FIG. 2. While the exposure time and the exposuredose were increased, the change of a variation in the dichloric ratioper unit exposure dose (mJ/cm²) as given by d(dichloric ratio)/d(mJ/cm²)was measured based on the total exposure dose of 500 mJ/cm² or moreafter the start of exposure and plotted in a graph as shown in FIG. 3.

Referring to FIG. 2, the photoreactive polymers according to theexamples had such an abrupt change in the dichloric ratio at the earlystage of the exposure that the maximum absolute value of d(dichloricratio)/d(mJ/cm²), a variation in the dichloric ratio per unit exposuredose (mJ/cm²), amounted to at least about 0.003 (e.g., about 0.0035 forExample 38, about 0.0059 for Example 59, or about 0.007 for Example 34)when the total exposure dose reached about 20 mJ/cm² immediately afterthe start of exposure. Referring to FIG. 3, there was little change inthe dichloric ratio that the absolute value of a variation in thedichloric ratio per unit exposure dose as given by d(dichloricratio)/d(mJ/cm²) was maintained in the range of about 0 to 0.00006, forexample, about 0 to 0.00002 even with a consistent increase in theexposure time and the total exposure dose once the total exposure dosereached a defined level.

Accordingly, the photoreactive polymers of the above examples had a veryhigh alignment rate in the early stage of the exposure and showed goodalignment stability that there was little change in the alignment rateonce a desired alignment characteristic was acquired. In contrast, thephotoreactive polymers of the comparative examples did not have such acharacteristic.

1. A photoreactive polymer comprising a cyclic olefin-based repeatingunit with at least one photoreactive substituent, the photoreactivepolymer being at least 0.003 in the maximum absolute value of avariation in dichloric ratio per unit UV dose as given by d(dichloricratio)/d(mJ/cm²) upon exposure to a polarized UV radiation having awavelength of 150 to 450 nm at a total exposure dose of 20 mJ/cm² orless.
 2. The photoreactive polymer as claimed in claim 1, wherein themaximum absolute value of a variation in dichloric ratio per unit UVdose as given by d(dichloric ratio)/d(mJ/cm²) is 0.003 to 0.008.
 3. Thephotoreactive polymer as claimed in claim 1, wherein the maximumabsolute value of a variation in dichloric ratio per unit UV dose asgiven by d(dichloric ratio)/d(mJ/cm²) upon exposure to a polarized UVradiation having a wavelength of 150 to 450 nm at a total exposure doseof 20 mJ/cm² is 0.003 to 0.008.
 4. The photoreactive polymer as claimedin claim 1, the photoreactive polymer absorbs a polarized UV radiationhaving a wavelength of 270 to 340 nm.
 5. The photoreactive polymer asclaimed in claim 1, wherein the absolute value of a variation indichloric ratio per unit UV dose as given by d(dichloricratio)/d(mJ/cm²) upon exposure to the polarized UV radiation at a totalexposure dose of 500 mJ/cm² or more is maintained in the range of 0 to0.00006.
 6. The photoreactive polymer as claimed in claim 5, wherein theabsolute value of a variation in dichloric ratio per unit UV dose asgiven by d(dichloric ratio)/d(mJ/cm²) upon exposure to the light at atotal exposure dose of 500 to 2,500 mJ/cm² is maintained in the range of0 to 0.00006.
 7. The photoreactive polymer as claimed in claim 1,wherein the cyclic olefin-based repeating unit comprises a repeatingunit of the following formula 3a or 3b:

wherein independently, m is 50 to 5,000; q is an integer from 0 to 4; atleast one of R1, R2, R3 and R4 is any one selected from the groupconsisting of radicals represented by the following formula 1a and 1b,among the R1 to R4, the remainders other than the radical of the formula1a or 1b are the same as or different from one another and independentlyselected from the group consisting of hydrogen; halogen; substituted orunsubstituted linear or branched alkyl having 1 to 20 carbon atoms;substituted or unsubstituted linear or branched alkenyl having 2 to 20carbon atoms; substituted or unsubstituted linear or branched alkynylhaving 2 to 20 carbon atoms; substituted or unsubstituted cycloalkylhaving 3 to 12 carbon atoms; substituted or unsubstituted aryl having 6to 40 carbon atoms; and a polar functional group comprising at least oneof oxygen, nitrogen, phosphor, sulfur, silicon, and boron, when the R1to R4 are not hydrogen, halogen, or a polar functional group, at leastone of a R1 and R2 coordination and a R3 and R4 coordination is bondedto each other to form an alkylidene group having 1 to 10 carbon atoms;or R1 or R2 is bonded to either R3 or R4 to form a saturated orunsaturated aliphatic ring having 4 to 12 carbon atoms or an aromaticring having 6 to 24 carbon atoms,

wherein A is chemical bond, oxygen, sulfur, or —NH—; B is selected fromthe group consisting of chemical bond, substituted or unsubstitutedalkylene having 1 to 20 carbon atoms, carbonyl, carboxy, ester,substituted or unsubstituted arylene having 6 to 40 carbon atoms, andsubstituted or unsubstituted heteroarylene having 6 to 40 carbon atoms;X is oxygen or sulfur; R9 is selected from the group consisting ofchemical bond, substituted or unsubstituted alkylene having 1 to 20carbon atoms, substituted or unsubstituted alkenylene having 2 to 20carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 12carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbonatoms, substituted or unsubstituted aralkylene having 7 to 15 carbonatoms, and substituted or unsubstituted alkynylene having 2 to 20 carbonatoms; at least one of R10 to R14 is a radical represented by-L-R15-R16-(substituted or unsubstituted C6-C40 aryl), among the R10 toR14, the remainders other than the radical of -L-R15-R16-(substituted orunsubstituted C6-C40 aryl) are the same as or different from one anotherand independently selected from the group consisting of hydrogen;halogen; substituted or unsubstituted alkyl having 1 to 20 carbon atoms;substituted or unsubstituted alkoxy having 1 to 20 carbon atoms;substituted or unsubstituted aryloxy having 6 to 30 carbon atoms;substituted or unsubstituted aryl having 6 to 40 carbon atoms; andheteroaryl having 6 to 40 carbon atoms with a hetero element in Group14, 15 or 16; L is selected from the group consisting of oxygen, sulfur,—NH—, substituted or unsubstituted alkylene having 1 to 20 carbon atoms,carbonyl, carboxy, —CONH—, and substituted or unsubstituted arylenehaving 6 to 40 carbon atoms; R15 is substituted or unsubstituted alkylhaving 1 to 10 carbon atoms; and R16 is selected from the groupconsisting of chemical bond, —O—, —C(═O)O—, —OC(═O)—, —NH—, —S—, and—C(═O)—.
 8. The photoreactive polymer as claimed in claim 7, wherein theradical of -L-R15-R16-(substituted or unsubstituted C6-C40 aryl) isrepresented by the following formula 2:

wherein R15 and R16 are as defined in formula 1; and R17 to R21 are thesame as or different from one another and independently selected fromthe group consisting of hydrogen; halogen; substituted or unsubstitutedalkyl having 1 to 20 carbon atoms; substituted or unsubstituted alkoxyhaving 1 to 20 carbon atoms; substituted or unsubstituted aryloxy having6 to 30 carbon atoms; substituted or unsubstituted aryl having 6 to 40carbon atoms; heteroaryl having 6 to 40 carbon atoms with a heteroelement in Group 14, 15 or 16; and substituted or unsubstitutedalkoxyaryl having 6 to 40 carbon atoms.
 9. The photoreactive polymer asclaimed in claim 7, wherein the polar functional group is selected fromthe group consisting of the following functional groups: —OR₆,—OC(O)OR₆,—R₅OC(O)OR₆, —C(O)OR₆, —R₅C(O)OR₆, —C(O)R₆, —R₅C(O)R₆, —OC(O)R₆,—R₅OC(O)R₆, —(R₅O)p-OR₆, —(OR₅)p-OR₆, —C(O)—O—C(O)R₆, —R₅C(O)—O—C(O)R₆,—SR₆, —R₅SR₆, —SSR₆, —R₅SSR₆, —S(═O)R₆, —R₅S(═O)R₆, —R₅C(═S)R₆,—R₅C(═S)SR₆, —R₅SO₃R₆, —SO₃R₆, —R₅N═C═S, —N═C═S, —NCO, —R₅—NCO, —CN,—R₅CN, —NNC(═S)R₆, —R₅NNC(═S)R₆, —NO₂, —R₅NO₂,

wherein independently, p is an integer from 1 to 10; R5 is substitutedor unsubstituted linear or branched alkylene having 1 to 20 carbonatoms; substituted or unsubstituted linear or branched alkenylene having2 to 20 carbon atoms; substituted or unsubstituted linear or branchedalkynylene having 2 to 20 carbon atoms; substituted or unsubstitutedcycloalkylene having 3 to 12 carbon atoms; substituted or unsubstitutedarylene having 6 to 40 carbon atoms; substituted or unsubstitutedcarbonyloxylene having 1 to 20 carbon atoms; or substituted orunsubstituted alkoxylene having 1 to 20 carbon atoms; and R6, R7 and R8are independently selected from the group consisting of hydrogen;halogen; substituted or unsubstituted linear or branched alkyl having 1to 20 carbon atoms; substituted or unsubstituted linear or branchedalkenyl having 2 to 20 carbon atoms; substituted or unsubstituted linearor branched alkynyl having 2 to 20 carbon atoms; substituted orunsubstituted cycloalkyl having 3 to 12 carbon atoms; substituted orunsubstituted aryl having 6 to 40 carbon atoms; substituted orunsubstituted alkoxy having 1 to 20 carbon atoms; and substituted orunsubstituted carbonyloxy having 1 to 20 carbon atoms.
 10. Thephotoreactive polymer as claimed in claim 7, wherein the photoreactivepolymer has a weight average molecular weight of 10,000 to 1,000,000.11. An alignment layer comprising the photoreactive polymer as claimedin claim
 1. 12. A display device comprising the alignment layer asclaimed in claim 11.